Process for the telomerization of a conjugated diene, catalyst and bidentate ligand useful therein

ABSTRACT

Process for the telomerization of a conjugated diene, 
     wherein the conjugated diene is reacted with a compound containing an active hydrogen atom and having a formula R′—H in the presence of a telomerization catalyst based on: 
     
         
         (a) a source of group VIII metal, 
         (b) a bidentate ligand
 
wherein the bidentate ligand has the general formula I
 
R 1 R 2 M 1 —R—M 2 R 3 R 4   (I)
 
wherein M 1  and M 2  are independently P, As or Sb; R 1 , R 2 , R 3  and R 4  independently represent a monovalent aliphatic group;
 
         or R 1 , R 2  and M 1  together and/or R 3 , R 4  and M 2  together independently represent an optionally substituted aliphatic cyclic group with at least 5 ring atoms, of which one is the M 1  or M 2  atom, respectively; 
         R represents a bivalent organic bridging group; and novel bidentate diphosphines which can be used in this process.

This application if a DIV of Ser. No. 10/287,731 filed on Nov. 4, 2002,now U.S. Pat. No. 6,794,553 which claims benefit of 60/348,205 filed onNov. 9, 2001.

FIELD OF THE INVENTION

The present invention relates to a process for the telomerization of aconjugated diene, and a catalyst and bidentate ligand that can be usedin this process.

BACKGROUND OF THE INVENTION

WO-A-9210450 describes a telomerization reaction wherein 1,3-butadieneis reacted with a compound containing an active hydrogen atom and havinga formula R—H in the presence of a telomerization catalyst to form a1-substituted-2,7-octadiene of formula CH₂═CH—CH₂—CH₂—CH₂—CH═CH—CH₂—R,in which R represent the residue of the compound containing an activehydrogen atom. WO-A-9210450 describes telomerization catalysts such asthe transition metals Fe, Co, Ni, Ru, Rh, Pd, Os, Ir and Pt (Group VIIItransition metals) and compounds thereof, including those supported onan inert carrier, as well as ligand compounds including diphosphines.

However, it is desirable to provide a process for the telomerization ofa conjugated diene, wherein the telomerization reaction can be carriedout with an improved selectivity towards the linear telomerizationproduct.

SUMMARY OF THE INVENTION

Accordingly, a process for the telomerization of a conjugated diene isprovided, comprising:

-   reacting the conjugated diene with a compound containing an active    hydrogen atom and having a formula R′—H in the presence of a    telomerization catalyst based on:-   (a) a source of group VIII metal,-   (b) a bidentate ligand    wherein the bidentate ligand has the general formula I    R¹R²M¹—R—M²R³R⁴  (I)    wherein M¹ and M² are independently P, As or Sb;-   R¹, R², R³ and R⁴ independently represent a monovalent aliphatic    group;-   or R¹, R² and M¹ together and/or R³, R⁴ and M² together    independently represent an optionally substituted aliphatic cyclic    group with at least 5 ring atoms, wherein one ring atom in said    cyclic group is M¹ or M²; and R represents a bivalent organic    bridging group.

In addition, a process for the preparation of 1-octene is provided,comprising:

-   a) reacting 1,3-butadiene with a compound containing an active    hydrogen atom and having a formula R′—H in the presence of a    telomerization catalyst based on:-   (1) a source of group VIII metal,-   (2) a bidentate ligand    wherein the bidentate ligand has the general formula I    R¹R²M¹—R—M²R³R⁴  (I)    wherein M¹ and M² are independently P, As or Sb;-   R¹, R², R³ and R⁴ independently represent a monovalent aliphatic    group;-   or R¹, R² and M¹ together and/or R³, R⁴ and M² together    independently represent an optionally substituted aliphatic cyclic    group with at least 5 ring atoms, wherein one ring atom in said    cyclic group is M¹ or M²; and R represents a bivalent organic    bridging group; thereby producing 1-substituted-2,7-octadiene;-   b) hydrogenating the 1-substituted-2,7-octadiene of step a), thereby    producing 1-substituted octane;-   c) decomposing the 1-substituted octane of step b), thereby    producing 1-octene.

Also provided are catalyst systems and bidentate ligands useful in theprocesses of the present invention.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 illustrates examples of one embodiment of the preparation ofligands.

DETAILED DESCRIPTION OF THE INVENTION

It has now been found that the telomerization of a conjugated diene canbe carried out with a high selectivity towards the linear telomerizationproduct in the presence of a specific catalyst system.

Accordingly, one embodiment of the present invention provides a processfor the telomerization of a conjugated diene, wherein the conjugateddiene is reacted with a compound containing an active hydrogen atom andhaving a formula R′—H in the presence of a telomerization catalyst basedon:

-   (a) a source of group VIII metal,-   (b) a bidentate ligand    wherein the bidentate ligand has the general formula I    R¹R²M¹—R—M²R³R⁴  (I)    wherein M¹ and M² are independently P, As or Sb;-   R¹, R², R³ and R⁴ independently represent a monovalent aliphatic    group;-   or R¹, R² and M¹ together and/or R³, R⁴ and M² together    independently represent an optionally substituted aliphatic cyclic    group with at least 5 ring atoms, of which one is the M¹ or M² atom,    respectively; and R represents a bivalent organic bridging group.

It has been found that the use of this specific catalyst system resultsin an improved selectivity towards the linear product whilst obtainingreaction rates well over 500 mol conjugated diene/mol group VIIImetal/hour.

The conjugated diene preferably is a conjugated diene having from 4 to20, more preferably from 4 to 8 carbon atoms per molecule. Theconjugated diene may be substituted or unsubstituted, and may contain anumber of heteroatoms. Examples of conjugated dienes that may be usedinclude 1,3-butadiene, isoprene, 1,3-pentadiene, and 1,3-hexadiene.Preferably the conjugated diene is unsubstituted and preferably theconjugated diene only contains carbon atoms. Most preferably, theconjugated diene is 1,3-butadiene.

In the telomerization process of 1,3-butadiene,1-substituted-2,7-octadiene can be prepared. 1-substituted-2,7-octadienecan be useful in a process to prepare 1-octene containing substantiallyno branched olefinic C₈-isomers. Therefore, a process for thepreparation of 1-octene is provided, comprising:

-   a) telomerization of 1,3-butadiene as described herein, to form    1-substituted-2,7-octadiene;-   b) hydrogenation of the 1-substituted-2,7-octadiene of step a) to    form 1-substituted octane;-   c) decomposition of the 1-substituted octane of step b) to form    1-octene.

Step a) of this process can be carried out as described herein. Steps b)and c) can be conveniently carried out as described in WO-A-9210450.

The conjugated diene used as a starting compound may contain smallamounts of other saturated or unsaturated hydrocarbons. For example, acrude C₄ hydrocarbon mixture may be used as a feed for 1,3-butadiene.Such a crude C₄ mixture may contain, besides 1,3-butadiene otherC₄-hydrocarbons such as butenes and butanes.

The active hydrogen-containing compound R′—H may be any compound havinga reactive hydrogen atom. Examples of such active hydrogen-containingcompounds include alkanols, hydroxy-aromatic compounds, carboxylicacids, ammonia, primary and secondary amines and water.

Preferred active hydrogen-containing compounds include water, alkanolsand hydroxy-aromatic compounds.

Alkanols that can be used in the process of the invention include mono-or poly alkanols, which can be linear or branched and saturated orunsaturated. Preferred alkanols for the process of the invention arealkanols with from 1 to 20, more preferably with from 1 to 6 carbonatoms per molecule and alkanediols with from 2 to 20, more preferablyfrom 2 to 6 carbon atoms per molecule. Suitable alkanols in the processof the invention include methanol, ethanol, ethanediol, propanol,1,2-propanediol, 1,3-propanediol, iso-propanol, butanol, 1,2-butanediol,1,4-butanediol, iso-butanol, tert-butanol, pentanol, hexanol,hexanediol, cyclohexanol, and cyclohexanediol. Of these, methanol,ethanol and phenol are preferred. Methanol and phenol are especiallypreferred.

Examples of hydroxy-aromatic compounds are aromatic compounds containingone or more rings such as phenol, benzylalcohol, cresols, xylenols,naphthol as well as polyhydric compounds such as resorcinol,hydroquinone and pyrocatechol. Also alkyl-, alkoxy- and/orhalogen-substituted aromatic hydroxy compounds may be used.

Examples of carboxylic acids that may be used in the process of theinvention include aliphatic carboxylic acids with up to about 20 carbonatoms. Preferred carboxylic acids are those having from 1 to 6 carbonatoms such as e.g. acetic acid, propionic acid, butyric acid. Examplesof suitable aromatic carboxylic acids include benzoic acid and toluenecarboxylic acid. Also carboxylic diacids can be used, such as forexample adipic acid and phthalic acid.

Examples of amine compounds that can be used in the process according tothe invention are ammonia and primary and secondary amines. Suitableamine compounds include for example primary aliphatic amines, such asmethylamine, ethylamine, butylamine, dodecylamine and the like; primaryaromatic amines, such as aniline, toluidine, benzylamine and the like;secondary amines such as dimethylamine, diethylamine, N-methylaniline,dicyclohexylamine, methylhexylamine, and the like; as well as polyaminesuch as phenylenediamine, ethylenediamine; and heterocyclic amines, suchas piperidine.

The telomerization reaction is carried out in the presence of certaincatalysts.

The group VIII metal is preferably selected from the metals rhodium,nickel, palladium and platinum. Of these, palladium and platinum arepreferred. Palladium is most preferred.

Examples of suitable metal sources are metallic platinum or palladiumand platinum or palladium on a carrier. Other suitable sources include,for example, platinum or palladium cation complexes which are convertedinto Pd (0) or Pt (0) during the reaction. Examples of such platinum orpalladium cation complexes include carboxylates of platinum orpalladium. A preferred source of palladium is tetrakis(dibenzylacetone)palladium.

The bidentate ligand has the general formula IR¹R²M₁—R—M²R³R⁴  (I)wherein M¹ and M² are independently P, As or Sb;

-   R¹, R², R³ and R⁴ independently represent a monovalent aliphatic    group;-   or R¹, R² and M¹ together and/or R³, R⁴ and M² together    independently represent an optionally substituted aliphatic cyclic    group with at least 5 ring atoms, of which one is the M¹ or M² atom,    respectively;-   and R represents a bivalent organic bridging group.

In the bidentate ligand of formula I, M¹ and M² are preferably the sameand more preferably they both represent phosphorus atoms.

The bivalent organic bridging group R preferably has from 1 to 6 andmore preferably from 2 to 6 atoms in the bridge. By “in the bridge” asused herein is understood to mean the shortest connection between theatoms M¹ and M².

Suitable bridging groups include substituted and unsubstituted alkylenegroups. The alkylene group can contain one or more hetero-atoms, such asSi, N, O, S, in the bridge, but preferably has only carbon atoms in thebridge. The alkylene group can be substituted with one or more groups,and is preferably substituted with two groups. The substituents cancontain one or more hetero-atoms. Examples of unsubstituted alkylenebridging groups include methylene, ethylene and tri-methylene groups.Examples of substituted alkylene bridging groups include for example2,2-dimethyl-trimethylene (i.e. neopentylene), 2,2-diethyl-trimethylene,2,2-dimethyl-tetramethylene, 2-methyl, 2-hydroxymethyl-trimethylene(i.e. neopentylol), 2,2 di-hydroxymethyl-trimethylene (i.e.neopentyldiol). Preferred alkylene bridging groups are ethylene,trimethylene and neopentylene groups, preferably connecting respectivelythe M¹ and M² atom by the first and the second or the third carbon atom,such as, for example, a 1,2-ethylene, a 1,3-trimethylene or a1,3-neopentylene group. Of these, neopentylene groups are especiallypreferred. Preferably the neopentylene bridging group is substitutedwith one or more hydroxy groups.

The bridging group can also comprise one or more aliphatic or aromaticring structures. Preferably such a bridging group still contains onlyfrom 2 to 6 carbon atoms in the bridge. An especially preferred bridginggroup contains two aromatic ring structures, preferably two benzenerings. These aromatic ring structures are preferably connected to eachother and to two alkylene groups which in their turn are connected torespectively M¹ and M².

The alkylene groups are preferably connected to the aromatic ringstructures at their ortho positions vis-à-vis the carbon atoms throughwhich the aromatic ring structures are connected.

In a preferred embodiment R¹, R², R³ and R⁴ independently represent aprimary, secondary or tertiary alkyl group. Preferably the alkyl grouphas from 1 to 10 carbon atoms, more preferably from 1 to 6 carbon atoms.Examples of such alkyl groups include methyl, ethyl, propyl, isopropyl,butyl, sec-butyl, iso-butyl, tert-butyl, pentyl, sec-pentyl,cyclopentyl, hexyl, cyclohexyl. Preferably R¹, R², R³ and R⁴independently represent a primary alkyl group. Examples of suitableprimary alkyl groups include methyl, ethyl and propyl. Preferably thegroups R¹ to R⁴ represent the same primary alkyl groups, most preferablyR¹ to R⁴ are methyl or ethyl groups.

In a further preferred embodiment R¹, R² and M¹ together and/or R³, R⁴and M² together independently represent an optionally substitutedaliphatic cyclic group with at least 5 ring atoms, of which one is theM¹ or M² atom, respectively.

By “a cyclic group” is understood a monocyclic or a polycyclic groupsuch as bicyclic or tricyclic groups. Preferred cyclic groups arebicyclic groups. The cyclic group contains at least one hetero-atom,i.e. the M¹ or M² atom, respectively, but can contain more hetero-atoms.Suitable hetero-atoms that can further be present in the cyclic groupinclude P, As, Sb, O, N, S and Si. The optionally substituted aliphaticcyclic group contains at least 5 ring atoms. Preferably the cyclic groupcontains from 6 to 20 ring atoms, more preferably from 6 to 12 ringatoms.

Preferably M¹ and M² are both phosphorus and R¹, R² and M¹ together andR³, R⁴ and M² together both represent a phosphabicycloalkyl group. In ahighly preferred embodiment the aliphatic cyclic group contains 9 ringatoms and forms a 9-phosphabicyclononyl group. The 9-phosphabicyclononylgroup can have several isomeric structures. For the purpose of theinvention the [3,3,1] and [4,2,1] isomers are preferred. R¹, R² and M¹together and/or R³, R⁴ and M² together can both have the same or eachhave a different isomeric structure. Preferably both R¹, R² and M¹together and/or R³, R⁴ and M² together have the [3,3,1] structure.

One or both of the phosphabicycloalkyl rings may be substituted with oneor more suitable hydrocarbyl groups containing carbon atoms and/orhetero-atoms. Suitable substituents include groups containinghetero-atoms such as halides, sulphur, phosphorus, oxygen and nitrogen.Examples of such groups include chloride, bromide, iodide, thiol, andgroups of the general formula —Y¹—OH, —Y¹—CO—OH, —Y¹—SH, —S—Y¹, —O—Y¹,—CO—Y¹, —NH₂, —NHY¹, —NY¹Y², —CO—N¹Y¹Y², —OH, —PO₄, —NO₂, —NOH, —CO,—SO₂, —S—OH, in which Y¹ and Y², independently, represent C₁–C₁₀ alkylgroups. If a phosphabicycloalkyl ring is substituted it is preferablysubstituted with a carbon containing group. Such a carbon containinggroup may, however, contain additional hetero-atoms, such as halides,sulphur, oxygen and nitrogen or hetero-groups as described hereinbefore.Preferably, substituted phosphabicycloalkyl rings are substituted withalkyl groups, preferably having from 1 to 10 carbon atoms, morepreferably from 1 to 4 carbon atoms. Linear, branched or cyclic alkylgroups can be used. Suitable alkyl groups include, methyl, ethyl,propyl, iso-propyl, butyl and iso-butyl. More suitably methyl groups areused. If the phosphabicycloalkyl ring is substituted, it may be mono- orpoly-substituted and is preferably di-substituted. More preferably thephosphabicycloalkyl ring in this case is substituted with two methylgroups. The phosphabicycloalkyl ring may be substituted at all carbonatoms of the ring. However, the use of rings with substituents oncertain carbon atoms may be more beneficial. Suitably,phosphabicyclononyl rings can be used with substituents on two carbonatoms, suitably carbon atom 1, 2, 8 and carbon atom 4, 5 or 6.

Examples of preferred bidentate ligands include

-   1,3-bis(diethylphosphino)-propane;-   1,3-bis(dimethylphosphino)-propane;-   1,3-bis-(1,4-cyclooctylene-phosphino)-propane, i.e.-   1,3-PP′bis(9-phosphabicyclo[4,2,1]nonyl)-propane;-   1,3-bis-(1,5-cyclooctylene-phosphino)-propane, i.e.-   1,3-PP′bis(9-phosphabicyclo[3,3,1]nonyl)-propane;-   1,2-bis-(1,4-cyclooctylene-phosphino)-ethane, i.e.-   1,2-PP′bis(9-phosphabicyclo[4,2,1]nonyl)-ethane;-   1,2-bis-(1,5-cyclooctylene-phosphino)-ethane, i.e.-   1,2-PP′-bis(9-phosphabicyclo[3,3,1]nonyl)-ethane;-   2,2-dimethyl, 1,3-PP′bis(9-phosphabicyclo-[3,3,1]nonyl)-propane;-   2-methyl, 2-hydroxymethyl,    1,3-PP′bis(9-phosphabicyclo[3,3,1]nonyl)-propane;-   2,2-dimethyl, 1,3-PP′bis(9-phosphabicyclo-[4,2,1]nonyl)-propane;-   2-methyl, 2-hydroxymethyl,    1,3-PP′bis(9-phosphabicyclo[4,2,1]nonyl)-propane;-   2,2′-bis-(1,4-cyclooctylene-phosphino-methyl)-1,1′-biphenyl;-   2,2′-bis-(1,5-cyclooctylene-phosphino-methyl)-1,1′-biphenyl;    and mixtures thereof.

Some of the bidentate ligands that can be used in the present inventionare considered to be novel.

The present invention therefore also relates to a bidentate ligand offormula II,R¹R²M¹—V—M²R³R⁴  (II)wherein M¹ and M² are independently P, As or Sb;

-   R¹, R², R³ and R⁴ independently represent a monovalent aliphatic    group;-   or R¹, R² and M¹ together and/or R³, R⁴ and M² together    independently represent an optionally substituted aliphatic cyclic    group with at least 5 ring atoms, of which one is the M¹ or M² atom,    respectively;-   and V represents a bridging group comprising a trimethylene group    connecting M¹ and M² of which the middle carbon atom has two    additional bondings with a non-hydrogen atom.-   R¹, R², M¹, M², R³ and R⁴ represent the same groups as described    hereinbefore. Preferences are as described hereinbefore.

V represents a bridging group comprising a tri-methylene groupconnecting M¹ or M² of which the middle carbon atom has two additionalbondings with a non-hydrogen atom. The middle carbon atom can have twoadditional bondings with one non-hydrogen atom, i.e. a double bond, orit can have two additional bondings with two separate non-hydrogenatoms.

Examples of non-hydrogen atoms to which the middle carbon group can bedouble bonded include hetero-atoms, such as oxygen, nitrogen, sulphur orsilicon. Furthermore the middle carbon atom can be double bonded toanother carbon atom.

Preferably, however, the middle carbon has two additional bondings withtwo separate non-hydrogen atoms. In a preferred embodiment the bridginggroup V represents a group having the formula—C(V1)—C(V3,V4)—C(V2)—  (IV)wherein V1 and V2 independently represent an optionally substitutedalkyl group having from 1 to 4 carbon atoms, such as methyl, ethyl,propyl and isopropyl, or hydrogen; and V3 and V4 independently representa non-hydrogen group.

V3 and V4 each can represent a separate group, or V3, V4 and the middlecarbon atom together can form a cyclic group.

If V3, V4 and the middle carbon atom together form a cyclic group, thecyclic group preferably comprises from 3 to 10 ring atoms, morepreferably from 3 to 6 ring atoms. The ring atoms can be hetero-atoms orcarbon atoms but are preferably carbon atoms.

Preferably, however, V3 and V4 each independently represent a separatehydrocarbyl group containing carbon atoms and/or hetero-atoms. Suitablehydrocarbyl groups for this purpose include groups containinghetero-atoms such as sulphur, phosphorus, oxygen and nitrogen. Examplesof such groups include groups of the general formula —X¹—OH, —X¹—CO—OH,—X¹—SH, —S—X¹, —O—X¹, —CO—X¹, —NH₂, —NHX¹, —NX¹X², —CO—NX¹X², —OH, —PO₄,—NO₂, —NOH, —CO, —SO₂, —S—OH, in which X¹ and X², independently,represent alkyl or alkylene groups having from 1 to 10 carbon atoms.Preferably V3 and/or V4 represent a carbon containing group. Such acarbon containing group may, however, contain additional hetero-atomssuch as halides, sulphur, oxygen and nitrogen or hetero groups asdescribed hereinbefore. Preferably V3 and/or V4 represent groups chosenfrom methyl, ethyl, propyl, hydroxymethyl and hydroxyethyl.

Preferred bidentate diphosphines according to formula II include

-   2,2-dimethyl-1,3-bis-(1,4-cyclooctylene-phosphino)-propane;-   2-methyl-2-hydroxymethyl-1,3-bis-(1,4-cyclooctylene-phosphino)-propane;-   2,2-dihydroxymethyl-1,3-bis-(1,4-cyclooctylene-phosphino)-propane;-   2,2-dimethyl-1,3-bis-(1,5-cyclooctylene-phosphino)-propane;-   2-methyl-2-hydroxymethyl-1,3-bis-(1,5-cyclooctylene-phosphino)-propane;-   2,2-dihydroxymethyl-1,3-bis-(1,5-cyclooctylene-phosphino)-propane.

These ligands can be prepared by:

-   i) reacting P-cyclo-octylene hydride (phosphabicyclo-nonane hydride)    and butyllithium to generate a lithium cyclo-octylene phosphide    (lithiated phosphabicyclo-nonane).-   ii) introducing a tosylate group to 3-methyl-3-oxetane methanol by    reaction with p-toluene sulfonyl chloride in dichloromethane as    solvent at 0° C. in the presence of pyridine.-   iii) reacting the phosphide of step i) with the tosylate substituted    oxetane of step ii), at for example 0° C. for the first phosphide    group and reflux conditions for the second phosphide group, in for    example tetrahydrofuran as a solvent.

An illustration of this reaction is given in FIG. 1.

The present invention further relates to a bidentate ligand of formula(III),Q¹Q²M¹—Q⁵—Ar¹—Ar²—Q⁶—M²Q³Q⁴  (III)wherein M¹ and M² are independently P, As or Sb;

-   Q¹, Q² and M¹ together and Q³, Q⁴ and M² together independently    represent an optionally substituted aliphatic cyclic group with at    least 5 ring atoms, of which one is the M¹ or M² atom, respectively;-   Q⁵ and Q⁶ each independently represent optionally substituted    alkylene groups;-   and Ar¹ and Ar² independently represent an optionally substituted    aromatic group.

M¹ and M² represent the same groups as described hereinbefore.Preferences are as described hereinbefore.

Q¹, Q² and M¹ together and Q³, Q⁴ and M² together independentlyrepresent an optionally substituted cyclic group with at least 5 ringatoms, of which one is the M¹ or M² atom, respectively. Preferences arethe same as for the cyclic groups represented by R¹, R² and M¹ together,and R³, R⁴ and M² together, respectively as described hereinbefore.

Q⁵ and Q⁶ each independently represent an optionally substitutedalkylene group. Preferably this alkylene group contains from 1 to 6,more preferably from 1 to 4 carbon atoms. The alkylene group can besubstituted with one or more hydrocarbyl groups. If the alkylene groupis substituted, it is preferably substituted with alkyl groups,preferably having from 1 to 6, more preferably from 1 to 4 carbon atoms.

Preferably the alkylene group is unsubstituted. Preferably both alkylenegroups are the same and preferably both alkylene groups areunsubstituted methylene or ethylene groups. Most preferably both Q⁵ andQ⁶ represent an unsubstituted methylene group.

Ar¹ and Ar² each independently represent an aromatic group. Preferablythe aromatic group contains from 6 to 20 carbon atoms, more preferablyfrom 6 to 14 carbon atoms. Examples of suitable aromatic groups includephenyl, naphthyl, phenanthryl and anthracenyl. Of these, phenyl groupsare preferred. The aromatic group can be substituted with one-or morehetero-atoms and/or hydrocarbyl groups. Hydrocarbyl groups used for thispurpose include alkyl, alkoxy and carbonyl groups. Preferably thearomatic group is unsubstituted. The aromatic groups are preferablyconnected with each other by the carbon atom next to the carbon atomattached to the alkylene group.

Preferred bidentate diphosphine according to formula III include

-   -   2,2′-bis-(1,4-cyclooctylene-phosphino-methyl)-1,1′-biphenyl;    -   2,2′-bis-(1,5-cyclooctylene-phosphino-methyl)-1,1′-biphenyl, and        mixtures thereof.

These ligands can be prepared by reacting P-cyclo-octylene hydride(phosphabicyclononane hydride) and butyllithium to generate a lithiumcyclo-octylene phosphide (lithiated phosphabicyclononane). The latterphosphide is reacted with a 2,2′-dimethyl-1,1′biphenyl group substitutedwith suitable leaving groups, preferably tosylates, mesylates andtriflates, in an appropriate manner. Preferred aliphatic groups arethose having a cyclic sulphate structure as a leaving group, such ascyclic substituted or unsubstituted alkane diol sulphate esters, alsocalled cyclic alkyl sulphates.

For example 2,2′-bis-(1,4-cyclooctylene-phosphino-methyl)-1,1′-biphenylcan be prepared by reacting phosphabicyclononane hydride andbutyllithium to generate the corresponding lithium phosphide andsubsequently reacting this lithium phosphide, at for example 0° C. intetrahydrofuran, with the di-p-tosylate ester of2,2′-dimethyl-1,′biphenyl wherein the tosylate groups are substituted onthe methyl groups.

The P-cyclo-octylene hydride (phosphabicyclononane hydride) mayconveniently be prepared as described by Elsner et al. (Chem. Abstr.1978, vol. 89, 180154x).

The present invention further provides a catalyst system comprising:

-   I) a source of group VIII metal;-   II) a bidentate ligand according to the general formula II or III as    described hereinbefore.    The catalyst system can be advantageously used for the    telomerization of conjugated dienes.

The amount of telomerization catalyst to be used is not critical, andany catalytically effective amount may be used. In general, amountsbetween about 0.000001 and about 1, and preferably between about0.000005 and about 0.01 gram atom of Group VIII metal per mole ofconjugated diene can be used. In order to achieve high catalystefficiencies without having to recycle the catalyst, amounts of lessthan 0.0001, preferably less than 0.00005, and more preferably less than0.00002 gram atoms of Group VIII metal are used per mole of conjugateddiene.

The bidentate ligand is generally used in a relative amount of fromabout 1 to about 20 moles, and preferably from about 2 to about 15 molesof bidentate ligand per gram atom of the Group VIII metal. The bidentateligand can be added as a separate compound to the reaction mixture orzone or to a catalyst make-up solution, or it may be incorporated in aGroup VIII metal complex.

Preferably, the process according to the present invention can beconducted in the substantial absence of oxygen, as oxygen reacts withthe bidentate ligand and consequently may result in decreased catalystactivity.

In the process, one or more of the reactants and/or the formed productmay act as reaction diluent. The reaction may also be carried out in theadditional presence of a solvent. As such, saturated hydrocarbons, e.g.paraffins and isoalkanes are preferred. Further suitable solventsinclude, for example, ethers such as 2,5,8-trioxanonane (diglyme),diethylether and anisole, and ketones, such as methylbutylketone.Solvents, comprising or substantially consisting of sulphones are alsopreferred. Sulphones are in particular preferred, for exampledialkylsulphones such as dimethylsulphone and diethylsulphone and cyclicsulphones, such as sulfolane (tetrahydrothiophene-2,2-dioxide),sulfolane, 2-methyl-sulfolane and 2-methyl-4-ethylsulfolane.

The temperature at which the telomerization reaction is carried out isnot critical. Normally, temperatures within the range of ambienttemperature to about 150° C. can be used. Preferably, the reactiontemperature is within the range of from about 40 to about 100° C. andmore preferably from about 50 to about 100° C.

The pressure at which the telomerization reaction is carried out is notcritical. Generally the reaction pressure is within the range of betweenabout 1 and about 10 bars.

The telomerization reaction can be carried out continuously, semi-batchor batch-wise.

In general, any conventional hydrogenation process can be used inpreparing 1-octene. The hydrogenation may be carried out in the liquidphase or in the vapor phase.

Depending on the nature of the starting material, the reaction can becarried out at a temperature between 0 and 400° C. Preferably thetemperature is in the range from ambient to 350° C. More preferably thehydrogenation is carried out at a temperature between 50 and 200° C. Thepressure is not critical and depends on whether the hydrogenation iscarried out in the liquid or vapor phase. In general the pressure canvary between 0.1 and 100 bar.

In process step (b) any of the conventional homogeneous andheterogeneous hydrogenation catalysts can be used. Examples of suchcatalysts include the Group VIII of the periodic system transition metalcatalysts. Preferred catalysts are the noble metal catalysts of thisgroup VIII, either in elemental form or in the form of a compound whichis reducible by hydrogen under hydrogenation conditions to form-f-inelydivided elemental metal, or mixtures thereof. Examples of such compoundsare the oxides, halides, nitrates, oxalates, acetates, carbamates,propionates, tartrates, hydroxides and the like or mixtures thereof.Preferred catalysts are palladium and platinum, whereas alsoRaney-nickel may advantageously be used. These catalysts may be modifiedwith other metals. The catalysts may preferably be supported on acarrier material, such as for example active carbon, alumina, silica,silica-alumina, calcium carbonate, barium carbonate, barium sulfate,clays, Kieselguhr and the like. Particularly preferred catalysts arealumina supported platinum or palladium catalysts, the metal preferablybeing dispersed on the support in an amount of 0.1 to 1.0 wtX.

The hydrogenation catalysts are used in the amounts conventional forthese type of reactions and catalysts.

Generally, the relative amounts of hydrogen, in the form of purehydrogen or as a hydrogen containing gas, and the1-substituted-2,7-octadiene are not critical, but it is preferred to usea molar ratio between hydrogen and the 1-substituted-2,7-octadiene inthe range from 2:1 to 50:1, more preferably from 2:1 to 10:1.

The hydrogenation can advantageously be carried out in a diluent orsolvent for dilution of the material to be hydrogenated. The usualdiluents may be used for this, such as saturated hydrocarbons having 4to 12 carbon atoms, alkanols containing from 1 to 12 carbon atoms,acyclic and cyclic ethers having 4 to 12 carbon atoms-and mixturesthereof. Advantageously, part of the reaction product of thehydrogenation reaction is recycled to step (b) and used as diluent inthe hydrogenation reaction.

The hydrogenation in step (b) can be carried out according to batch,semi-continuous or continuous procedures. It may also be performed inmore than one step, such as for example in a preliminary hydrogenationstep and a finishing hydrogenation step. Typical weight hourly spacevelocities (based on reactant) are in the range of 0.1–50, preferably inthe range of 0.2–10 and more preferably in the range of 0.5–5.

In the decomposition process step (c), of the present invention anysuitable conventional catalyst can be used which is capable ofdecomposing the 1-substituted octane to give 1-octene. Generally, asolid acidic catalyst is used for this purpose. Preferably an aluminacatalyst is used. Examples of such catalysts are alpha, delta, gamma,etha and theta-aluminas, which may be modified with metal-containingweakly acidic components, organic carboxylic acids, or other treatingagents.

The temperatures at which the decomposition process is carried outdepend on the decomposition temperature of the respective compound andon the catalyst activity. Generally the temperatures are up to 500° C.,preferably in the range of 200 to 400° C., whereas temperatures in therange of 250 to 350° C. are more preferred.

The pressure under which the decomposition reaction may be carried outis not critical and can vary widely, for example from 0.1 to about 50bar.

Preferably the reaction is carried out at a pressure between 0.2 and 10bar.

The reaction can be carried out in the vapor or in the liquid phase, thevapor phase being preferred.

An inert carrier gas or an inert diluent may be used to dilute thereactant. Examples of such inert gases are nitrogen, helium, argon andthe like or mixtures thereof.

The reaction may be carried out continuously, semi-continuously orbatchwise. In the continuous mode the reactant(s) and possibly thediluent are continuously passed over a bed of the catalyst at thedesired reaction conditions. The reactant is generally added to thereactor containing the catalyst under the desired reaction conditions ata weight hourly space velocity of about 0.01 to about 50, and preferablyabout 0.1 to about 10.

The desired product 1-octene may be recovered from the reaction mixtureusing conventional methods such as solvent extraction, (fractional)distillation, (fractional) condensation etc.

The invention will be illustrated by the following non-limitingexamples.

EXAMPLES 1–9 AND COMPARATIVE EXAMPLE A

The experiments were carried out in a 250 ml Hastelloy C autoclave. Thetelomerization catalyst was prepared separately as a 5 ml methanolsolution of 0.25 mmol Pd(dibenzylacetone)₂ and 0.3 mmol bidentate ligandas given in Table I. The catalyst solution was introduced under anitrogen atmosphere to a medium of alkanol and optionally additionalinert solvent in the autoclave as indicated in Table I. The autoclavewas closed, evacuated and 15 ml 1,3 butadiene was pumped in.

Subsequently, the reactor was sealed and the contents were heated to atemperature as specified in Table I. The temperature was maintainedduring the reaction time as specified in Table I. Thereafter theautoclave was cooled to room temperature and the contents were analyzedby standard GLC. The obtained reaction rate and selectivity towards thelinear 1-substituted 2,7-octadiene are given in Table I. Generatedby-products included vinylcyclohexene and mono-butenyl ethers.

The mono-butenyl ethers can be very useful in a wide range of otherapplications. The reaction rate is defined as the average rate over 90%butadiene conversion.

TABLE I Selectivity Reaction Reaction towards linear Bidentate time ratetelomerization Example Medium ligand Temperature (hours) (mol/mol/hr)product 1 20 ml methanol/ BDEPP 70 0.5 1400 91.5 40 ml diglyme 2 20 mlmethanol/ BDEPP 70 0.5 1000 90 40 ml NMP 3 20 ml methanol/ BDMPP 70 0.252000 94 40 ml diglyme 4 20 ml methanol/ BCOPP 70 1.5 500 93 40 mldiglyme 5 50 ml methanol MHBCOPP 70 0.25 3000 95 6 50 ml methanol BCOPE70 0.25 2000 94 7 50 g phenol/ BCOPE 60 0.5 1500 90 40 ml diglyme 8 50ml methanol 1,4 BCOPMB 70 increased n.d. n.d. 96¹ to 85 9 50 ml methanol1,5 BCOPMB 70 n.d. n.d. 92² A 50 ml methanol DPPP 70 5 n.d. —³ n.d. =not determined BDEPP = 1,3-bis(diethylphosphino)-propane BDMPP =1,3-bis(dimethylphosphino)-propane BCOPP = mixture of 1,3-bis(1,4-cyclo-octylenephosphino) propane and1,3-bis(1,5-cyclo-octylenephosphino) propane BCOPE = mixture of 1,2-bis(1,4-cyclo-octylenephosphino) ethane and1,2-bis(1,5-cyclo-octylenephosphino) ethane MHBCOPP = 2-methyl,2-hydroxymethyl, 1,3-bis (1,4-cyclo-octylenephosphino) propane 1,4BCOPMB = 2,2′-bis-(1,4-cyclooctylene-phosphino-methyl)-1,1′-biphenyl 1,5BCOPMB = 2,2′-bis-(1,5-cyclooctylene-phosphino-methyl)-1,1′-biphenyl NMP= N-methyl-2-pyrrolidone DPPP = 1,3-bis(diphenylphosphino)-propane ¹=only 4% telomerization product was formed,whereas 59% mono-butenylethers were formed ²= only 31% telomerization product was formed,whereas59% mono-butenyl ethers were formed ³= only traces of ethers were formed

1. A process for the telomerization of a conjugated diene comprisingreacting the conjugated diene with a compound containing an activehydrogen atom, wherein said compound is selected from the groupconsisting of alkanols, hydroxyl-aromatic compounds, carboxylic acids,ammonia, primary amines, secondary amines, and water, in the presence ofa telomerization catalyst based on: (a) a source of group VIII metal,(b) a bidentate ligand wherein the bidentate ligand has the generalformula IR¹R²M¹—R—M²R³R⁴  (I) wherein M¹ and M² are independently P, As or Sb;R¹, R², R³ and R⁴ independently represent a monovalent aliphatic group;or R¹, R² and M¹ together and/or R³, R⁴ and M² together independentlyrepresent an optionally substituted aliphatic cyclic group with at least5 ring atoms, wherein one ring atom in said cyclic group is M¹ or M²;and R represents a bivalent organic bridging group.
 2. The process ofclaim 1 wherein the conjugated diene is 1,3-butadiene.
 3. The process ofclaim 1 wherein the active hydrogen-containing compound is selected fromthe group consisting of water, an alkanol, and an hydroxy-aromaticcompound.
 4. The process of claim 2 wherein the activehydrogen-containing compound is selected from the group consisting ofwater, an alkanol and an hydroxy-aromatic compound.
 5. The process ofclaim 1 wherein the bidentate ligand is selected from the groupconsisting of 1,3-bis(diethylphosphino)-propane;1,3-bis(dimethylphosphino)-propane;1,3-bis-(1,4-cyclooctylene-phosphino)-propane;1,3-PP′bis(9-phosphabicyclo[4,2,1]nonyl)-propane;1,3-bis-(1,5-cyclooctylene-phosphino)-propane;1,3-PP′bis(9-phosphabicyclo[3,3,1]nonyl)-propane;1,2-bis-(1,4-cyclooctylene-phosphino)-ethane;1,2-PP′bis(9-phosphabicyclo[4,2,1]nonyl)-ethane;1,2-bis-(1,5-cyclooctylene-phosphino)-ethane;1,2-PP′bis(9-phosphabicyclo[3,3,1]nonyl)-ethane; 2,2-dimethyl,1,3-PP′bis(9-phosphabicyclo[3,3,1]nonyl)-propane; 2-methyl,2-hydroxymethyl, 1,3-PP′bis(9-phosphabicyclo[3,3,1]nonyl)-propane;2,2-dimethyl, 1,3-PP′bis(9-phosphabicyclo[4,2,1]nonyl)-propane;2-methyl, 2-hydroxymethyl,1,3-PP′bis(9-phosphabicyclo[4,2,1]nonyl)-propane;2,2′-bis-(1,4-cyclooctylene-phosphino-methyl)-1,1′-biphenyl;2,2′-bis-(1,5-cyclooctylene-phosphino-methyl)-1,1-biphenyl.
 6. Theprocess of claim 1 wherein the bidentate ligand has the general formulaII,R¹R²M¹—V—M²R³R⁴(II) wherein M¹ and M² are independently P, As or Sb; R¹,R², R³ and R⁴ independently represent a monovalent aliphatic group; orR¹, R² and M¹ together and/or R³, R⁴ and M² together independentlyrepresent an optionally substituted aliphatic cyclic group with at least5 ring atoms, wherein one ring atom in said cyclic groups is M¹ or M²;and V represents a bridging group comprising a trimethylene groupconnecting M¹ and M² of which the middle carbon atom has two additionalbondings with a non-hydrogen atom.
 7. The process of claim 6 wherein thetrimethylene group middle carbon atom is double bonded to a hetero-atomselected from the group consisting of oxygen, nitrogen, sulphur, andsilicon.
 8. The process of claim 6 wherein the trimethylene group middlecarbon atom is double bonded to another carbon atom.
 9. The process ofclaim 6 wherein the trimethylene group middle carbon atom has twoadditional bondings with two separate non-hydrogen atoms.
 10. Theprocess of claim 6 wherein the bidentate ligand is selected from thegroup consisting of2,2-dimethyl-1,3-bis-(1,4-cyclooctylene-phosphino)-propane;2-methyl-2-hydroxymethyl-1,3-bis-(1,4-cyclooctylene-phosphino)-propane;2,2 dihydroxymethyl-1,3-bis-(1,4-cyclooctylene-phosphino)-propane;2,2-dimethyl-1,3-bis-(1,5-cyclooctylene-phosphino)-propane;2-methyl-2-hydroxymethyl-1,3-bis-(1,5-cyclooctylene-phosphino)-propane;and 2,2 dihydroxymethyl-1,3-bis-( 1,5-cyclooctylene-phosphino)-propane.11. The process of claim 1 wherein the bidentate ligand has the generalformula (III),Q¹Q²M¹—Q⁵—Ar¹—Ar²—Q⁶—M²Q³Q⁴  (III) wherein M¹ and M² are independentlyP, As or Sb; Q¹, Q² and M¹ together and Q³, Q⁴ and M² togetherindependently represent an optionally substituted aliphatic cyclic groupwith at least 5 ring atoms, wherein one ring atom in said cyclic groupis M¹ or M²; Q⁵ and Q⁶ each independently represent optionallysubstituted alkylene groups; and Ar¹ and Ar² independently represent anoptionally substituted aromatic group.
 12. The process of claim 11wherein the bidentate ligand is2,2′-bis-(1,4-cyclooctylene-phosphino-methyl)-1,1′-biphenyl or2,2′-bis-(1,5-cyclooctylene-phosphino-methyl)-1,1′biphenyl.